Process for producing bio-resourced polymer-grade acrylic acid from glycerol

• US 8,748,545 B2
• Filed: 09/14/2009
• Issued: 06/10/2014
• Est. Priority Date: 09/16/2008
• Status: Expired due to Fees

• Current Assignee: Arkema France (Arkema)
• Original Assignee: Arkema France (Arkema)
• Inventors: Devaux, Jean-Francois, Fauconet, Michel, Laurent, Denis
• Primary Examiner(s): CHU, YONG LIANG
• Application Number:
  US13/119,066
• Publication Number:
  US 20120108767A1
• Time in Patent Office: 1,730 Days
• Field of Search: 526/75, 526/317.1, 526/532
• US Class Current: 526/75
• CPC Class Codes: C07C 45/52 by dehydration and rearrangement involving two hydroxy groups in the same molecule
• CPC Class Codes: C07C 47/22 Acryaldehyde; Methacryaldehyde
• CPC Class Codes: C07C 51/235 of —CHO groups or primary alcohol groups
• CPC Class Codes: C07C 51/252 of propene, butenes, acrolein or methacrolein
• CPC Class Codes: C07C 51/44 by distillation
• CPC Class Codes: C07C 51/46 by azeotropic distillation
• CPC Class Codes: C07C 51/48 by liquid-liquid treatment
• CPC Class Codes: C07C 51/487 by treatment giving rise to chemical modification by chemisorption C07C51/47
• CPC Class Codes: C07C 57/04 Acrylic acid; Methacrylic acid
• CPC Class Codes: C08F 20/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
• CPC Class Codes: C08F 220/06 Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof

Abstract

The present invention relates to the manufacture of bioresourced polymer-grade acrylic acid from glycerol. The polymer grade acrylic acid produced has limited content of certain impurities harmful to polymerization processes, such as, total aldehydes, protoanemonin, maleic anhydride and nonphenolic polymerization inhibitors. The invention also relates to the use of the bioresourced acrylic acid obtained for manufacture of superabsorbents or for manufacture of polymers or copolymers using amide or ester derivatives of the bioresourced acrylic acid.

Claims

1. A process for manufacturing polymer grade acrylic acid using naturally renewable starting materials comprising at least the steps of:

i) dehydrating glycerol to form acrolein;

ii) oxidizing the acrolein to form acrylic acid;

iii) extracting the acrylic acid by countercurrentwise absorption and forming an aqueous acrylic acid solution;

iv) dehydrating the aqueous acrylic acid solution in the presence of at least one solvent to form an acrylic acid mixture, wherein the solvent is immiscible with water and capable of forming an azeotrope with water;

v) removing one or more light compounds from the acrylic acid mixture by distillation;

vi) removing one or more heavy impurities from the acrylic acid mixture by distillation to form a technical grade of acrylic acid; and

vii) purifying by distilling the technical grade of acrylic acid and adding at least one amino compound which reacts with aldehydes in the technical grade acrylic acid to form polymer grade acrylic acid, wherein the polymer grade acrylic acid contains greater than 99% by weight of acrylic acid, less than 5 ppm protoanemonin, less than 10 ppm total aldehydes, less than 30 ppm maleic anhydride, less than 10 ppm nonphenolic polymerization inhibitors, and a content by weight of ¹⁴C such that the ¹⁴C/¹²C ratio is greater than 0.8×

10<sup>−

12</sup>.

2. The process of claim 1, wherein step iii) employs water as an absorption solvent.

3. The process of claim 1, wherein during step iii), the absorption is coupled with a column for distillation of light compounds.

4. The process of claim 1, wherein step iv) is carried out by a liquid/liquid extraction comprising an organic phase, followed by separation of the acrylic acid present in the organic phase by distillation.

5. The process of claim 1 wherein step iv) is carried out by azeotropic distillation.

6. The process of claim 1 wherein step iv), is coupled to a column for recovery of the solvent.

7. The process of claim 1 wherein the solvent in step iv) is methyl isobutyl ketone (MIBK).

8. The process of claim 1, wherein the step vii) purification is carried out using two distillation columns.

9. The process of claim 1 wherein the amino compound is a hydrazine derivative.